EP2501769B1 - Haftklebstoff mit an acrylpolymer wasserstoffbrücken-gebundenem funktionalisiertem polyisobutylen - Google Patents

Haftklebstoff mit an acrylpolymer wasserstoffbrücken-gebundenem funktionalisiertem polyisobutylen Download PDF

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Publication number
EP2501769B1
EP2501769B1 EP10779192.3A EP10779192A EP2501769B1 EP 2501769 B1 EP2501769 B1 EP 2501769B1 EP 10779192 A EP10779192 A EP 10779192A EP 2501769 B1 EP2501769 B1 EP 2501769B1
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Prior art keywords
pressure sensitive
sensitive adhesive
adhesive composition
polyisobutylene
acrylate
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French (fr)
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EP2501769A1 (de
Inventor
Vivek Bharti
Guy D. Joly
Shujun Wang
Peiwang Zhu
Babu N. Gaddam
Sanat Mohanty
Jingjing Ma
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2421/00—Presence of unspecified rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]

Definitions

  • PSAs Pressure sensitive adhesives
  • thermoplastic vulcanizates In recent years, there has been a significant increase in the use of plastics, vulcanized rubbers, and thermoplastic vulcanizates ("TPV”) in the automotive, appliance and electronics markets. Generally, these materials combine the desirable characteristics of vulcanized rubber with the processing ease of thermoplastics.
  • TSV thermoplastic vulcanizates
  • bonding to these and other low surface energy substrates currently requires priming the substrate surface prior to bonding with a pressure sensitive adhesive (“PSA”). The priming process can be expensive and labor intensive, and may present environmental concerns.
  • a pressure sensitive adhesive composition comprising a polyisobutylene polymer having a first functional group and an acrylic polymer having a second functional group present in the acrylic polymer backbone.
  • the first and second functional groups form a hydrogen bond.
  • the adhesive composition further comprises a crosslinker that covalently crosslinks the second functional group(s) present in the polymer backbone of the acrylic polymer.
  • a pressure sensitive adhesive coated article such as a tape.
  • the article comprises a substrate and the pressure sensitive adhesive described herein coated on at least one surface of the substrate.
  • a method of bonding comprising providing a substrate, applying the adhesive on a surface of the substrate, and contacting the pressure sensitive adhesive with another substrate.
  • a method of making a pressure sensitive adhesive comprises blending a polyisobutylene polymer having a first functional group; and an acrylic polymer having a second functional group present in the polymer backbone; wherein the first and second functional groups form a hydrogen bond.
  • pressure-sensitive adhesive refers to adhesive compositions that have (1) aggressive and persistent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be cleanly removable from the adherend.
  • the pressure sensitive adhesive composition described herein comprises at least one polyisobutylene (PIB) polymer having a first functional group, also referred to herein as the "functionalized polyisobutylene".
  • the first functional group is typically a terminal group.
  • the first functional group can form a hydrogen bond to (e.g. pendant carboxylic acid groups of) the backbone of an acrylic polymer or a functional group appended to the (e.g. backbone) of the acrylic polymer.
  • the functionalized polyisobutylene polymer is a functionalized homopolymer of isobutylene.
  • the functionalized polyisobutylene polymer may be a copolymer comprising isobutylene repeat units and a small amount of units derived from another monomer such as, for example, styrene, isoprene, butene, or butadiene.
  • These copolymers are typically prepared from a monomer mixture that includes at least 70 weight percent, at least 75 weight percent, at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, or at least 95 weight percent isobutylene based on the weight of monomers in the monomer mixture.
  • At least 70 weight percent, at least 75 weight percent, at least 80 weight percent, at least 85 weight percent, or at least 90 weight percent of the polyisobutylene copolymer is formed from isobutylene repeat units.
  • Exemplary copolymers include isobutylene copolymerized with isoprene.
  • the functionalized polyisobutylene is typically a liquid polymer having a relatively low to intermediate number average (M n ) molecular weight.
  • M n is typically at least 500 g/mole, 750 g/mole, or about 1,000 g/mole.
  • the M n of the functionalized polyisobutylene is no greater than 25,000 g/mole, or 10,000 g/mole, or 5,000 g/mole.
  • the functionalized polyisobutylene typically has a glass transition temperature of no greater than about -30°C or less, no greater than about -50°C, or no greater than about - 70°C, as determined by differential scanning calorimetry (DSC).
  • the functional group of the functionalized polyisobutylene can be any functional group that forms a hydrogen bond with (e.g. pendant carboxylic acid groups of) the backbone of an acrylic polymer or a functional group appended to the (e.g. backbone) of the acrylic polymer.
  • the predominant bond between the functional group of the polyisobutylene and the acrylic polymer is a hydrogen bond.
  • a hydrogen bond is an attractive force, or bridge, occurring in polar compounds in which a hydrogen atom of one molecule or functional group is attracted to unshared electrons of another.
  • the hydrogen atom is the positive end of one polar molecule or functional group (otherwise known as a hydrogen bond donor) and forms a linkage with the electronegative end of another molecule or functional group (otherwise known as a hydrogen bond acceptor).
  • Functional groups that have non-polar covalent bonds do not form hydrogen bonds.
  • Common hydrogen-bond donors include carboxylic acids, phosphonic acids, phosphoric acid esters, sulfonic acids, sulfinic acids, alcohols, and phenols.
  • Common hydrogen-bond acceptors include nitrogen containing groups such as amines, amides, imines, imides, nitriles and ureas as well as aromatic nitrogen-based functional groups such as pyridines, imidazoles, etc.
  • Other hydrogen-bond acceptors include carboxylate groups (carboxylic acid, carboxylic ester), phosphonates, sulfoxides, sulfones, and carbamates.
  • the acrylic polymer has carboxylic acid functionality and the functionalized PIB has a functional (e.g. terminal) group that hydrogen bonds with the carboxylic acid group of the acrylic polymer or a functional group appended to the (e.g. backbone) of the acrylic polymer.
  • a functional (e.g. terminal) group that hydrogen bonds with the carboxylic acid group of the acrylic polymer or a functional group appended to the (e.g. backbone) of the acrylic polymer.
  • the functional group of the functionalized PIB is not acrylate, methacrylate, or any other functional group that covalently bonds with a (meth)acrylate group via a free radical polymerization.
  • This approach can be preferred since it can utilize commercially available functionalized PIB having a terminal nitrogen containing group such as an amine or imide.
  • PIB materials are commercially available.
  • polyisobutene succinimide is available from BASF under the trade designation "Kerocom® PIBSI”.
  • An anhydride-terminated polyisobutylene (M n ) of about 1,000 grams/mole) is available from BASF under the trade designation "Glissopal SA”.
  • the commercially available functionalized PIB materials are suitable for the formation of hydrogen bonds wherein the carboxylic acid group is the proton donor (i.e. H-bond donor) and the nitrogen-containing group (i.e. amine or imide) is the proton acceptor (i.e. H-bond acceptor).
  • the carboxylic acid group is the proton donor (i.e. H-bond donor) and the nitrogen-containing group (i.e. amine or imide) is the proton acceptor (i.e. H-bond acceptor).
  • the functionalized PIB may have a (e.g. terminal) carboxylic acid group, provided that the carboxylic acid groups of the acrylic polymer are pre-reacted to convert these groups to a functional group that will then in turn form a hydrogen bond with the carboxylic acid groups of the PIB.
  • polyisobutyleneamine e.g. Kerocom ® PIBA03
  • anhydride such as succinic anhydride or glutaric anhydride
  • a carboxylic acid-functionalized PIB could also be prepared by reaction of anhydride-terminated polyisobutylene (e.g. Glissopal SA) with an alcohol (such as 1-octanol) to provide a PIB chain terminated with an ester and a carboxylic acid.
  • anhydride-terminated polyisobutylene e.g. Glissopal SA
  • an alcohol such as 1-octanol
  • Amine-functionalized acrylic polymers can be prepared by copolymerization of at least one amino comonomer with alkyl (meth)acrylate monomers.
  • Suitable amino comonomers are olefinically unsaturated, polymerizable compounds that contain at least one primary or secondary amino group, e.g. amino methacrylates such as tert-butylaminoethyl methacrylate or meta-isopropenyl- ⁇ , ⁇ -dimethylbenzylamine.
  • Amino groups can also be obtained by the reaction of acid polymers with aziridines such as ethylene imine, as well as other techniques known for adding amine functionality to polymers.
  • N,N-dimethylaminopropyl methacrylamide DMAPMAm
  • DMAPPMAm N,N-diethylaminopropyl methacrylamide
  • DAEA N,N-diethylaminoethyl acrylate
  • DEAEA N,N-dimethylaminopropyl acrylate
  • DMAPA N,N-diethylaminopropyl acrylate
  • DEAPA N,N-dimethylaminoethyl methacrylate
  • DMAEMA N,N-diethylaminoethyl methacrylate
  • DEAEMA N,N-dimethylaminoethyl acrylamide
  • DMAEMAm N,N-dimethylaminoethyl methacrylamide
  • DMAEMAm N,N-diethylaminoethyl acrylamide
  • tertiary amino-functionalized styrene e.g., 4-(N,N-dimethylamino)-styrene (DMAS), 4-(N,N-dimethylamino)-styrene (DEAS)
  • DMAS 4-(N,N-dimethylamino)-styrene
  • DAS 4-(N,N-dimethylamino)-styrene
  • DEAS 4-(N,N-dimethylamino)-styrene
  • hydroxy-functionalized PIBs can be prepared by various methods as known in the art.
  • hydroxy-functionalized PIBs could also be synthesized by reacting anhydride-terminated polyisobutylene (e.g. Glissopal SA) with amino alcohols or diols, or by reacting polyisobutyleneamine (e.g. Kerocom ® PIBA03) with 2-chloroethanol or epoxides.
  • Pyridine-functionalized PIB-based materials can be synthesized by reacting an amino or hydroxy-bearing pyridine compound with a polyisobutylene (e.g. succinic) anhydride (e.g. Glissopal ® SA).
  • polyisobutyleneamine e.g. Kerocom ® PIBA03
  • 3-(chloromethyl)pyridine e.g. 3-(chloromethyl)pyridine
  • Carbamate-functionalized PIB could be obtained by reacting polyisobutyleneamine (e.g. Kerocom ® PIBA03) with isocyanate electrophiles.
  • the presence and concentration of functional groups within a functionalized PIB material can be determined by Proton Nuclear Magnetic Resonance.
  • the functionalized PIB material comprises at least 3 mol-% of functional groups.
  • the concentration of functional groups is generally no greater than 10 mol-%.
  • the amount of functionalized PIB material in the pressure sensitive adhesive composition can vary depending on the desired end use of the adhesive composition.
  • the concentration of functionalized PIB material is at least 2 wt-%, or 5 wt-%, or 10 wt-% in order to improve adhesion with low surface energy substrates such as those prepared from polyolefins.
  • the concentration of functionalized PIB material may range up to 40 wt-%, or 50 wt-%, or 60 wt-%. Particularly when the pressure sensitive adhesive composition is also intended for use with higher surface energy substrates, the concentration of functionalized PIB material is typically 40 wt-% to 60 wt-%, when utilizing a functionalized PIB material having a relatively low molecular weight (e.g. M n less than 10,000 g/mole).
  • the pressure sensitive adhesive composition described herein further comprises at least one acrylic polymer.
  • the acrylic polymer generally comprises the reaction product of at least one alkyl (meth)acrylate and at least one comonomer, most commonly a carboxylic acid, that provides functional groups along the backbone of the acrylic polymer.
  • the acrylic copolymer of the adhesive composition comprises at least about 70 wt-%, in some embodiments, at least about 80 wt-%, at least about 90 wt-%, at least about 95 wt-%, or even about 98 wt-% of at least one alkyl (meth)acrylate.
  • the alkyl (meth)acrylate contains 4 to 20 carbon atoms, e.g., 4 to 8 carbon atoms.
  • Exemplary alkyl (meth)acrylate include isooctyl acrylate (IOA), 2-octyl acrylate (2-OA), 2-ethylhexyl acrylate (2-EHA), butyl acrylate (BA), isobornyl acrylate (IBA), and combinations thereof.
  • the acrylic copolymer utilized in the PSA comprises at least two of such alkyl (meth)acrylates such as isooctyl acrylate and isobornyl acrylate.
  • acrylic copolymer of the adhesive composition comprises no greater than 10 parts of comonomer, such as carboxylic acid. Since the comonomer typically provides the functional groups that compliment the functionality of the polyisobutylene, the concentration of comonomer is typically at least 0.5, 1, 2, 3, 4, or 5 wt-%. Exemplary comonomers include carboxylic acids such as acrylic acid or methacrylic acid.
  • a comonomer (e.g. (meth)acrylate acid) concentration of 5 wt-% to 10 wt-% or 15 wt-% provides increased cohesive strength, as evident by the shear values.
  • the amount of acrylic polymer in the pressure sensitive adhesive composition can vary depending on the desired end use of the adhesive composition. Typically, however, the concentration of acrylic polymer is at least 20 wt-% or 25-wt-%. The concentration of acrylic polymer may range up to 50 wt-% or 60 wt-%. Particularly when the pressure sensitive adhesive composition is also intended for use with both low and higher surface energy substrates, the concentration of acrylic polymer typically ranges from 40 wt-% to 60 wt-%, when utilizing a functionalized PIB material having a relatively low molecular weight (e.g. M n less than 10,000 g/mole).
  • M n relatively low molecular weight
  • the alkyl (meth)acrylate monomer(s) and functionalizing comonomer(s) are prepolymerized into an acrylic polymer and then combined with the functionalized PIB.
  • the alkyl (meth)acrylate monomer(s) and functionalizing comonomer(s) are combined with the functionalized PIB and then the monomers are polymerized.
  • the alkyl (meth)acrylate monomers and functionalized PIB can be polymerized by use of a thermal initiator or photoinitiator.
  • the thermal initiator is often a peroxide, hydroperoxide, or azo compound.
  • the alkyl(meth)acrylate monomers can be polymerized using ultraviolet radiation by use of an alpha-cleavage type photoinitiator including but not limited to benzoin or benzoin alkyl ethers.
  • the functionalized PIB lacks functional groups that covalently copolymerize with the alkyl (meth)acrylate monomer(s) and functionalizing monomer(s), either method of preparation results in a composition comprising a blend of functionalized polyisobutylene polymer and acrylic polymer wherein the polyisobutylene polymer is hydrogen bonded to the functional groups along the backbone of the acrylic polymer.
  • reaction product of the functionalized PIB and the acrylic polymer can be represented as follows, wherein Z represents a hydrogen-bond between complimentary functional groups:
  • the adhesive may comprise solely the functionalized PIB hydrogen bonded to the acrylic polymer, in the absence of crosslinker or any other optional components.
  • the adhesives of the present disclosure may be crosslinked to improve their mechanical properties.
  • chemical crosslinking is preferred to improve the cohesive strength (as indicated by the static shear) of the pressure sensitive adhesive.
  • the adhesive may comprise a chemical crosslinker that is suitable for crosslinking the (e.g. carboxylic acid) functional groups of the acrylic polymer with each other.
  • Suitable crosslinkers are known in the art such as aziridine or bisaziridine crosslinkers.
  • One suitable bisaziridine crosslinker is prepared as described in U.S. Provisional Application No. 61/158,485, filed March 9, 2009 (Peiwang Zhu et al . AZIRIDINE CROSSLINKING AGENTS FOR ACRYLIC ADHESIVES).
  • the reaction product of the functionalized PIB and the acrylic polymer can be represented as follows:
  • the concentration of chemical crosslinker in the pressure sensitive adhesive composition is typically at least 0.025 wt-% and no greater than 2 wt-%.
  • the adhesive further comprises at least one unfunctionalized (e.g. PIB) synthetic rubber material.
  • the unfunctionalized (e.g. PIB) synthetic rubber material typically has substantially higher molecular weight than the functionalized (e.g. PIB) polyisobutylene material.
  • the weight average molecular weight (M w ) of the unfunctionalized (e.g. PIB) synthetic rubber material is at least 75,000 grams per mole, at least 100,000 grams per mole, e.g., at least 250,000 grams per mole, at least 500,000 grams per mole, or even at least 1,000,000 grams per mole.
  • the weight average molecular weight is typically no greater than 4,000,000 g/mole.
  • the unfunctionalized (e.g. PIB) synthetic rubber material can be a homopolymer, copolymer, or a mixture thereof. Copolymers can be random or block copolymers. Block copolymers can include the polyisobutylene sections in the main backbone, in a side chain, or in both the main backbone and a side chain of the polymeric material.
  • the polyisobutylene material is typically prepared by polymerizing isobutylene alone or by polymerizing isobutylene plus additional ethylenically unsaturated monomers in the presence of a Lewis Acid catalyst such as aluminum chloride, boron trichloride (with titanium tetrachloride as a cocatalyst), or boron trifluoride.
  • a Lewis Acid catalyst such as aluminum chloride, boron trichloride (with titanium tetrachloride as a cocatalyst), or boron trifluoride.
  • Unfunctionalized polyisobutylene materials are commercially available from several manufacturers. Homopolymers are commercially available, for example, under the trade designation OPPANOL (e.g., OPPANOL B10, B15, B30, B50, B100, B150, and B200) from BASF Corp. (Florham Park, NJ). These polymers often have a weight average molecular weight (M w ) in the range of about 40,000 to 4,000,000 grams per mole. Still other exemplary homopolymers are commercially available from United Chemical Products (UCP) of St. Moscow, Russia in a wide range of molecular weights.
  • OPPANOL e.g., OPPANOL B10, B15, B30, B50, B100, B150, and B200
  • M w weight average molecular weight
  • Still other exemplary homopolymers are commercially available from United Chemical Products (UCP) of St. Russia in a wide range of molecular weights.
  • homopolymers commercially available from UCP under the trade designation SDG have a viscosity average molecular weight (M v ) in the range of about 35,000 to 65,000 grams per mole.
  • Homopolymers commercially available from UCP under the trade designation EFROLEN have a viscosity average molecular weight in the range of about 480,000 to about 4,000,000 grams per mole.
  • Homopolymers commercially available from UCP under the trade designation JHY have a viscosity average molecular weight (M v ) in the range of about 3000 to about 55,000 grams per mole.
  • These homopolymers typically do not have reactive double bonds. It is appreciated that the unfunctionalized (e.g.
  • PIB PIB synthetic rubber
  • the concentration of such reactive double bonds or other functional groups is typically less than 5, 4, 3, or 2 mol%.
  • Such olefinic unsaturations are generally non-polar and thus not suitable functional groups for the formation of hydrogen bonds.
  • the concentration of unfunctionalized (e.g. PIB) synthetic rubber material in the pressure sensitive adhesive composition is typically at least 5 wt-%, 10 wt-%, or 20 wt-% and no greater than 50 wt-% or 60 wt-%.
  • the adhesive may comprise the functionalized (e.g. PIB) polyisobutylene hydrogen bonded to the acrylic polymer, optionally crosslinker, and an unfunctionalized low molecular weight polyisobutylene material.
  • the adhesive composition further comprises both a high molecular weight unfunctionalized (e.g. PIB) synthetic rubber and an unfunctionalized low molecular weight polyisobutylene materials.
  • the low molecular weight (e.g. PIB) synthetic rubber materials are liquids at room temperature and can function as a plasticizer with a variety of elastomeric materials.
  • such polyisobutylene materials have number average molecular weight of no greater than 10,000 g/mole, e.g., no greater than 5,000 g/mole, or even no greater than 2,000 g/mole.
  • the number average molecular weight is typically at least about 500 g/mole or 1000 g/mole.
  • the ratio of the weight average molecular weight to the number average molecular weight is typically in the range of about 1.6 to 2.0.
  • Exemplary low molecular weight polyisobutylene homopolymers are commercially available under the trade designation GLISSOPAL (e.g., GLISSOPAL 1000, 1300, and 2300) from BASF Corp. (Florham Park, NJ). These polyisobutylene materials usually have terminal double bonds and are considered to be reactive polyisobutylene materials.
  • GLISSOPAL e.g., GLISSOPAL 1000, 1300, and 2300
  • the concentration of unfunctionalized low molecular weight polyisobutylene (e.g. PIB) material in the pressure sensitive adhesive is typically at least 5 wt-%, 10 wt-% or 20 wt-% and no greater than 30 wt-%.
  • the adhesive may comprise the functionalized (e.g. PIB) polyisobutylene hydrogen bonded to the acrylic polymer, optionally crosslinker, optionally high/and or low molecular weight unfunctionalized (e.g. PIB) polyisobutylene materials, in the absence of any tackifier(s) or plasticizer(s).
  • the adhesive comprises at least one tackifier(s), plasticizer(s), or mixtures thereof.
  • the tackifier can have any suitable softening temperature or softening point.
  • the softening temperature is often less than 200°C, less than 180°C, less than 160°C, less than 150°C, less than 125°C, or less than 120°C.
  • the tackifier is often selected to have a softening point of at least 75°C.
  • Such a softening point helps minimize separation of the tackifier from the rest of the adhesive composition when the adhesive composition is subjected to heat such as from an electronic device or component.
  • the softening temperature is often selected to be at least 80°C, at least 85°C, at least 90°C, or at least 95°C. In applications that do not generate heat, however, the tackifier can have a softening point less than 75°C.
  • Exemplary tackifiers include hydrocarbon resins and hydrogenated hydrocarbon resins, e.g., hydrogenated cycloaliphatic resins, hydrogenated aromatic resins, or combinations thereof.
  • Suitable tackifiers are commercially available and include, e.g., those available under the trade designation ARKON (e.g., ARKON P or ARKON M) from Arakawa Chemical Industries Co., Ltd.
  • ESCOREZ e.g., ESCOREZ 1315, 1310LC, 1304, 5300, 5320, 5340, 5380, 5400, 5415, 5600, 5615, 5637, and 5690
  • REGALREZ e.g., REGALREZ 1085, 1094, 1126, 1139, 3102, and 6108 from Eastman Chemical, Kingsport, TN.
  • the concentration of tackifier can vary depending on the intended adhesive composition. In some embodiments, the amount of tackifier is at least 10 wt-% or 20 wt-%. The maximum amount of tackifier is typically no greater than 40 wt-%, 50 wt-%, or 60 wt-%.
  • additives can include, for example, initiators, ultraviolet absorbents (e.g., benzotriazole, oxazolic acid amide, benzophenone, or derivatives thereof), ultraviolet stabilizers (e.g., hindered amines or derivatives thereof, imidazole or derivatives thereof, phosphorous-based stabilizers, and sulfur ester-based stabilizers), antioxidants (e.g., hindered phenol compounds, phosphoric esters, or derivatives thereof).
  • ultraviolet absorbents e.g., benzotriazole, oxazolic acid amide, benzophenone, or derivatives thereof
  • ultraviolet stabilizers e.g., hindered amines or derivatives thereof, imidazole or derivatives thereof, phosphorous-based stabilizers, and sulfur ester-based stabilizers
  • antioxidants e.g., hindered phenol compounds, phosphoric esters, or derivatives thereof.
  • Exemplary antioxidants include those available from Ciba Specialty Chemicals In
  • the adhesives of the present disclosure may be combined with a substrate to form any number of typical adhesive articles, e.g., single- and double-coated tapes, and laminating adhesives.
  • laminating adhesives may comprise either a free film of adhesive or an adhesive film embedded with a support, e.g., a woven or non-woven scrim.
  • Such products can be formed by applying (e.g., coating, casting, or extruding) the adhesive onto a release liner, and drying and/or curing the adhesive.
  • the adhesives of the present disclosure may also be applied to one or both sides of a substrate to form a single- or double-coated tape.
  • Any know substrate including single and multi-layer substrates comprising one or more of paper, polymeric film, and metal (e.g., metal foil) may be used.
  • one or more layers of the substrate may be foam.
  • one or both adhesive layers may be bonded directly to the substrate.
  • one or both adhesive layers may be indirectly bonded to the substrate.
  • one or more intermediate layers e.g., primer layers
  • the adhesive is useful for bonding to a variety of metal and polymeric materials.
  • Metals typically have a surface energy of at least about 500 dynes/cm (0.5 N/m).
  • stainless steel is reported to have a surface energy of about 700-1100 dynes/cm (0.7-1.1 N/m).
  • Inorganic oxides generally have a surface energy less than that of metals.
  • glass is reported to have a surface energy of about 250-500 dynes/cm (0.25-0.5 N/m).
  • the adhesive is particularly useful for bonding to various polymeric materials.
  • Polymeric materials such as plastics generally have a surface energy of less than 100 dynes/cm, 75 dynes/cm, or 50 dynes/cm (0.1 N/m, 0.075 N/m, or 0.05 N/m)
  • polyester is reported to have surface energy of 43 dynes/cm (0.0043 N/m); polycarbonate 42 dynes/cm (0.042 N/m); polyvinyl chloride 39 dynes/cm (0.039 N/m); and acrylic 38 dynes/cm (0.038 N/m)
  • Even lower surface energy materials have a surface energy of less than 37 dynes/cm (0.037 N/m).
  • These include for example polyvinyl acetate, polystyrene, acetal, ethylene vinyl acetate, and polyethylene, reported to have a surface energy of 31 dynes/cm (0.031 N/m).
  • the pressure sensitive adhesive can exhibit various peel and shear properties, depending on the intended end use.
  • the 90 degree peel to glass, stainless steel, high density polyethylene (HDPE), polypropylene (PP), or EPDM is at least 5 oz/inch (5 N/dm) for a temporary removable or low temperature PSA.
  • the 90 degree peel to glass, stainless steel, HDPE, PP, or EPDM is typically 15-20 oz/inch (16-22 N/dm).
  • the 90 degree peel to glass, stainless steel, HDPE, or PP is at least 50, 60, 70, 80 or 90 oz/inch (55, 66, 77, 88 or 99 N/dm).
  • the shear at room temperature (23°C) is at least 300 minutes, 500 minutes, or 800 minutes.
  • the adhesive exhibits good adhesion to both high and low surface energy substrates.
  • the 90 degree peel to glass or stainless steel is at least 50, 60, 70, 80 or 90 oz/inch (55, 66, 77, 88 or 99 N/dm) in combination with the 90 degree peel to PP being at least 30, 40, 50, or 60 oz/inch (33, 44, 55, or 66 N/dm).
  • the 90 degree peel to EPDM is typically at least 30,40, or 50 oz/inch (33, 44, or 55 N/dm); whereas the 90 degree peel to HDPP is at least 30, 40, or 50 oz/inch (33, 44, or 55 N/dm) .
  • the shear at room temperature (23°C) or 70°C is at least 2,000 minutes; 4,000 minutes; 8,000 minutes; or 10,000 minutes.
  • test panels included: Material Description Source EPDM Ethylene/propylene-diene class M rubber; having a durometer hardness of 60, measuring 5.1 x 12.7 x 0.15 cm (2 x 5 x 0.059 in.); available as EPDM, Part No. RZW07-015 Zatkoff Seals & Packings, Warren, MI PP Polypropylene (0.91 g/cc) (Quadrant EPP Proteus Natural Homopolymer Polypropylene); Stainless Steel SS, 304, 18 gauge stainless steel, bright annealed finish.
  • test panels were cleaned with a 1:1 isopropyl alcohol/ water mixture and thoroughly dried prior to use.
  • the peel tests were performed after a 15 min dwell time in a controlled environment room on the test panel, unless otherwise stated.
  • the average peel adhesion force required to remove the tape from the panel was measured in ounces and is expressed in Oz/inch, based on 2 test samples.
  • Static Shear Strength at 23°C/50 % Relative Humidity Evaluation of static shear strength was performed as described in the ASTM International standard, D3654, Procedure A, with a 1.3 cm x 2.5 cm (1/2 in. x 1 in.) test specimen and a 1000 g load. The test panels were stainless steel ("SS"). Time to failure in minutes was recorded. If no failure was observed after 10,000 minutes, the test was stopped and a value of >10,000 minutes was recorded.
  • Static Shear Strength at 70°C Evaluation of static shear strength was performed as described in the ASTM International standard, D3654, Procedure A, with a 1.3 cm x 2.5 cm (1/2 in. x 1 in.) test specimen and a 500 g load. The test panels were stainless steel ("SS"). Time to failure in minutes was recorded. If no failure was observed after 10,000 minutes, the test was stopped and a value of >10,000 minutes was recorded.
  • Crosslinker 2 1,1'-isophthaloyl-bis(2-methylaziridine) crosslinker (CAS No. 7652-64-4) as described in US Patent No. 6893718 .
  • Example 1 PIBA03 55.4 Acrylic Copolymer (98:02 IOA/AA, 26% solids in EtOAc/Heptane) 44.6 E1310 0.0 Crosslinker (15 wt% in toluene) 0.0
  • Example 2 PIBA03 55.4 Acrylic Copolymer (94:06 IOA/AA, 45% solids in EtOAc/Heptane) 44.6 E1310 0.0 Crosslinker (15 wt% in toluene) 0.0
  • Example 3 PIBA03 55.1 Acrylic Copolymer (98:02 IOA/AA, 26% solids in EtOAc/Heptane) 44.6 E1310 0.0 Crosslinker (15 wt% in toluene) 0.5
  • Example 4 PIBA03 55.1 Acrylic Copolymer (94:06 IOA/AA, 45% solids in EtOAc/Heptane) 44.6 E1310 0.0 Crosslinker (15 wt% in toluene) 0.5
  • Example 5 PIBA03
  • Example 1 1.2 Glass 11 (12) SS 15 (16) HDPE 7 (8) Example 2 1.2 Glass 12 (13) SS 8 (9) HDPE 2 (2) Example 3 1.2 Glass 10 (11) SS 13 (14) HDPE 10 (11) Example 4 1.2 Glass 9 (10) SS 8 (9) HDPE 2 (2) Example 5 2.5 Glass 92 (101) SS 87 (95) HDPE 58 (64) Example 6 3.5 Glass 79 (86) SS 78 (85) HDPE 81 (89) Example 7 3.5 Glass 68 (75) SS 70 (77) HDPE 69 (76) Example 8 2.0 HDPE 36 (40) Example 9 2.0 HDPE 92 (101) Example 10 2.7 HDPE 14 (15)
  • the reaction was placed in a water bath/shaker at 65°C and gently agitated. After 63 hours, the reaction was removed from the water bath and was allowed to cool to room temperature. A viscous solution of the acrylic polymer in ethyl acetate was obtained.
  • Adhesive compositions further comprising unfunctionalized PIB were prepared according to the following procedure: Kerocom ® PIBA03 was added to a glass vial. Next, the isooctyl acrylate/acrylic acid copolymer solution (e.g. 94:6 isooctyl acrylate:acrylic acid or 90:10 isooctyl acrylate:acrylic acid in a 35% wt% ethyl acetate solution) was added, followed by adding unfunctionalized PIB (in a 15wt% toluene solution) with tackfier (e.g. E1310). Additional toluene was added to make the total solids concentration equal 35 wt%.
  • Kerocom ® PIBA03 was added to a glass vial.
  • the isooctyl acrylate/acrylic acid copolymer solution e.g. 94:6 isooctyl acrylate:acrylic acid or 90
  • the concentration of each component in the various formulations is illustrated in the tables.
  • the components were mixed well by shaking until the solution turned translucent and the components were uniformly dispersed.
  • bisaziridine crosslinker (a 15 wt% solution in toluene) was added and the formulation was again shaken and mixed well.
  • a hand spread was pulled onto a silicone release liner (Silphan S36 M74A) using a 9 mill gap (0.2286 mm).
  • the film was dried in an oven at 70°C for 30 minutes.
  • the adhesive film was allowed to cool to room temperature.
  • the adhesive film was 0.0019" thick.
  • 2 mil (0.0020") thick anodized aluminum was laminated on the PSA tape as adhesive backing.

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Claims (15)

  1. Haftklebstoffzusammensetzung, umfassend:
    ein Polyisobutylenpolymer mit einer ersten funktionalen Gruppe; und
    ein Acrylpolymer mit einer zweiten funktionalen Gruppe, die in der Acrylpolymer-Hauptkette vorliegt;
    wobei die erste und die zweite funktionale Gruppe eine Wasserstoffbindung bilden.
  2. Haftklebstoffzusammensetzung nach Anspruch 1, wobei die erste oder die zweite funktionale Gruppe ein Wasserstoffbindungsakzeptor ist und die jeweils andere funktionale Gruppe ein Wasserstoffbindungsdonor ist.
  3. Haftklebstoffzusammensetzung nach Anspruch 1, wobei das Polyisobutylen ein zahlenmittleres Molekulargewicht von weniger als 10.000 g/mol aufweist.
  4. Haftklebstoffzusammensetzung nach Anspruch 1, wobei das Polyisobutylen ein zahlenmittleres Molekulargewicht von weniger als 15.000 g/mol aufweist.
  5. Haftklebstoffzusammensetzung nach Anspruch 1, wobei die erste oder die zweite funktionale Gruppe ein Amin oder Imid ist und die jeweils andere funktionale Gruppe eine Carbonsäure ist.
  6. Haftklebstoffzusammensetzung nach Anspruch 1, wobei das Acrylpolymer ein Copolymer von mindestens einem Alkyl(meth)acrylat und mindestens einer Carbonsäure ist.
  7. Haftklebstoffzusammensetzung nach Anspruch 6, wobei es sich bei dem Alkyl(meth)acrylat um ein C4- bis C20-Alkyl(meth)acrylat handelt.
  8. Haftklebstoffzusammensetzung nach Anspruch 6, wobei es sich bei dem Alkyl(meth)acrylat um ein C4- bis C8-Alkyl(meth)acrylat handelt.
  9. Haftklebstoffzusammensetzung nach Anspruch 1, wobei die Klebstoffzusammensetzung ferner einen chemischen Vernetzer umfasst, der die in der Polymer-Hauptkette des Acrylpolymers vorliegenden zweiten funktionalen Gruppen kovalent vernetzt.
  10. Haftklebstoffzusammensetzung nach Anspruch 9, wobei der Vernetzer ausgewählt ist aus einem Aziridinvernetzer.
  11. Haftklebstoffzusammensetzung nach einem der vorstehenden Ansprüche, wobei die Zusammensetzung ferner unfunktionalisiertes Polyisobutylen umfasst.
  12. Haftklebstoffzusammensetzung nach Anspruch 11, wobei das unfunktionalisierte Polyisobutylen ein gewichtsmittleres Molekulargewicht im Bereich von 75.000 g/mol bis 4.000.000 g/mol aufweist.
  13. Haftklebstoffzusammensetzung nach Anspruch 11 oder 12, wobei die Zusammensetzung ein unfunktionalisiertes Polyisobutylen mit einem zahlenmittleren Molekulargewicht von weniger als 10.000 g/mol umfasst.
  14. Haftklebstoffzusammensetzung nach einem der vorstehenden Ansprüche, ferner umfassend ein klebrig machendes Harz, einen Weichmacher oder ein Gemisch davon.
  15. Artikel, umfassend:
    ein Substrat; und
    den Haftstoffkleber nach einem der vorstehenden Ansprüche, der auf mindestens einer Seite des Substrats aufgebracht ist.
EP10779192.3A 2009-11-19 2010-11-15 Haftklebstoff mit an acrylpolymer wasserstoffbrücken-gebundenem funktionalisiertem polyisobutylen Not-in-force EP2501769B1 (de)

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US26261309P 2009-11-19 2009-11-19
PCT/US2010/056648 WO2011062852A1 (en) 2009-11-19 2010-11-15 Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer

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EP2501769B1 true EP2501769B1 (de) 2015-01-21

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WO2008066914A1 (en) 2006-11-30 2008-06-05 The University Of Akron Polyisobutylenes and process for making same
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WO2009148722A2 (en) 2008-06-02 2009-12-10 3M Innovative Properties Company Adhesive encapsulating composition and electronic devices made therewith
JP5270755B2 (ja) 2008-06-02 2013-08-21 スリーエム イノベイティブ プロパティズ カンパニー 接着剤封入組成物及びそれで作られた電子デバイス
WO2010002557A1 (en) 2008-07-02 2010-01-07 3M Innovative Properties Company Low surface energy adhesive
JP2010163566A (ja) 2009-01-16 2010-07-29 Three M Innovative Properties Co エポキシ樹脂組成物
EP2406338B1 (de) 2009-03-09 2012-11-28 3M Innovative Properties Company Aziridine als vernetzungsmittel für acrylklebstoffe
CN102459485B (zh) 2009-06-04 2014-08-27 3M创新有限公司 可拉伸剥离压敏粘合剂
TW201111463A (en) 2009-08-04 2011-04-01 3M Innovative Properties Co Non-halogentaed polyisobutylene-thermoplastic elastomer blend pressure sensitive adhesives
KR20120089343A (ko) 2009-11-19 2012-08-09 쓰리엠 이노베이티브 프로퍼티즈 컴파니 아크릴 중합체에 결합된 작용화 합성 고무와 합성 고무의 블렌드를 포함하는 감압 접착제
EP2652060B1 (de) 2010-12-13 2017-02-22 3M Innovative Properties Company Druckempfindliche klebstoffe für niedrigenergiesubstrate

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Publication number Priority date Publication date Assignee Title
WO2021079229A1 (en) * 2019-10-24 2021-04-29 3M Innovative Properties Company Transparent solvent-based acrylic pressure-sensitive adhesive agent and adhesive film

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US20120285618A1 (en) 2012-11-15
EP2501769A1 (de) 2012-09-26
JP5695658B2 (ja) 2015-04-08
US8992720B2 (en) 2015-03-31
WO2011062852A1 (en) 2011-05-26
JP2013511594A (ja) 2013-04-04
CN102666764B (zh) 2015-09-30
KR20120101076A (ko) 2012-09-12
CN102666764A (zh) 2012-09-12

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